C‐Alkylation of Ketones and Related Compounds by Alcohols: Transition‐Metal‐Catalyzed Dehydrogenation

Angewandte Chemie International Edition, Год журнала: 2015, Номер 55(3), С. 862 - 875

Опубликована: Дек. 7, 2015

Transition-metal-catalyzed C-alkylation of ketones and secondary alcohols, with avoids use organometallic or environmentally unfriendly alkylating agents by means borrowing hydrogen (BH) autotransfer (HA) activation the alcohol substrates. Water is formed as only by-product, thus making BH process atom-economical benign. Diverse homogeneous heterogeneous transition-metal catalysts, ketones, alcohols can be used for this transformation, rendering promising replacing those procedures that traditional agents. This Minireview summarizes advances during last five years in transition-metal-catalyzed α-alkylation β-alkylation alcohols. A discussion on application strategy C-C bond formation included.

Язык: Английский

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Manganese‐Catalyzed Multicomponent Synthesis of Pyrimidines from Alcohols and Amidines

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(6), С. 1663 - 1666

Опубликована: Янв. 12, 2017

Abstract The development of catalytic reactions for synthesizing different compounds from alcohols to save fossil carbon feedstock and reduce CO 2 emissions is high importance. Replacing rare noble metals with abundantly available 3d equally important. We report a manganese‐complex‐catalyzed multicomponent synthesis pyrimidines amidines up three alcohols. Our reaction proceeds through condensation dehydrogenation steps, permitting selective C−C C−N bond formations. β‐Alkylation are used multiply alkylate secondary two primary synthesize fully substituted in one‐pot process. PN 5 P‐Mn‐pincer complexes efficiently catalyze this A comparison our manganese catalysts related cobalt indicates that shows reactivity similar iridium but not cobalt. This analogy could be develop further (de)hydrogenation complexes.

Язык: Английский

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Manganese‐Catalyzed Sustainable Synthesis of Pyrroles from Alcohols and Amino Alcohols

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(25), С. 7261 - 7265

Опубликована: Май 16, 2017

The development of reactions that convert alcohols into important chemical compounds saves our fossil carbon resources as can be obtained from indigestible biomass such lignocellulose. conservation rare noble metals is similar importance, and their replacement by abundantly available transition metals, Mn, Fe, or Co (base nonprecious metals), in key technologies catalysis a promising option. Herein, we report on the first base-metal-catalyzed synthesis pyrroles amino alcohols. most efficient catalysts are Mn complexes stabilized PN5 P ligands whereas related Fe inactive. reaction proceeds under mild conditions at catalyst loadings low 0.5 mol %, has broad scope attractive functional-group tolerance. These findings may inspire others to use replace Ir Ru challenging dehydrogenation reactions.

Язык: Английский

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A Reusable Co Catalyst for the Selective Hydrogenation of Functionalized Nitroarenes and the Direct Synthesis of Imines and Benzimidazoles from Nitroarenes and Aldehydes

Angewandte Chemie International Edition, Год журнала: 2016, Номер 55(48), С. 15175 - 15179

Опубликована: Окт. 31, 2016

Abstract The use of abundantly available transition metals in reactions that have been preferentially mediated by rare noble metals, for example, hydrogenations, is a desirable aim catalysis and an attractive strategy element conservation. observation novel selectivity patterns with such inexpensive metal catalysts especially appealing. Herein, we report novel, robust, reusable cobalt catalyst permits the selective hydrogenation nitroarenes presence highly hydrogenation‐sensitive functional groups, as well direct synthesis imines from aldehydes or ketones substituents. Furthermore, introduce first base‐metal‐mediated benzimidazoles aldehydes. Functional groups are easy to hydrogenate again tolerated.

Язык: Английский

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Transition metals-catalyzed amination of biomass feedstocks for sustainable construction of N-heterocycles

Coordination Chemistry Reviews, Год журнала: 2023, Номер 502, С. 215622 - 215622

Опубликована: Дек. 26, 2023

Язык: Английский

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Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia

Nature Communications, Год журнала: 2016, Номер 7(1)

Опубликована: Окт. 20, 2016

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges this century. The reversible hydrogen covalently bound in chemical compounds is particularly promising technology. For this, that can be sustainably synthesized permit high-weight% would highly desirable. Herein, we report catalytically modified lignin, an indigestible, abundantly available hitherto barely used biomass, harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which able hydrogenate dehydrogenate N-heterocycles most efficiently. Furthermore, particular N-heterocycle identified one step from main lignin hydrogenolysis product ammonia, new allows multiple cycles storage. Energy two major for sustainability. Here authors use synthesis develop repeated hydrogenation/dehydrogenation other molecules

Язык: Английский

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Ruthenium-Catalyzed Amination of Secondary Alcohols Using Borrowing Hydrogen Methodology

ACS Catalysis, Год журнала: 2016, Номер 6(4), С. 2205 - 2210

Опубликована: Фев. 23, 2016

A new ruthenium complex catalyzes the amination of primary and secondary alcohols regioselective mono- sequential diamination diols via borrowing hydrogen pathway. Several variations on intra- intermolecular cyclizations aminoalcohols, diols, diamines lead to heterocyclic ring systems.

Язык: Английский

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Acceptorless dehydrogenative coupling reactions with alcohols over heterogeneous catalysts

Green Chemistry, Год журнала: 2018, Номер 20(13), С. 2933 - 2952

Опубликована: Янв. 1, 2018

Recent examples for the acceptorless dehydrogenative coupling reactions of alcohols over heterogeneous catalysts one-pot synthesis value-enhanced chemicals are reviewed.

Язык: Английский

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Ligand-Controlled Copper(I)-Catalyzed Cross-Coupling of Secondary and Primary Alcohols to α-Alkylated Ketones, Pyridines, and Quinolines

Organic Letters, Год журнала: 2018, Номер 20(3), С. 608 - 611

Опубликована: Янв. 16, 2018

One hexanuclear Cu(I) cluster of 4,6-dimethylpyrimidine-2-thiolate efficiently catalyzes the dehydrogenative cross-coupling secondary and primary alcohols to α-alkylated ketones with high selectivity. This transformation proceeds through a one-pot sequence dehydrogenation alcohols, condensation aldehydes ketones, hydrogenation resulting α,β-unsaturated generate ketones. catalytic system also displays activity for annulation reaction γ-amino- 2-aminobenzyl yield pyridines quinolines, respectively.

Язык: Английский

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A Ruthenium Catalyst with Unprecedented Effectiveness for the Coupling Cyclization of γ-Amino Alcohols and Secondary Alcohols

ACS Catalysis, Год журнала: 2016, Номер 6(2), С. 1247 - 1253

Опубликована: Янв. 12, 2016

The ruthenium complex (8-(2-diphenylphosphinoethyl)aminotrihydroquinolinyl)(carbonyl)(hydrido)ruthenium chloride exhibited extremely high efficiency toward the coupling cyclization of γ-amino alcohols with secondary alcohols. corresponding products, pyridine or quinoline derivatives, are obtained in good to isolated yields. On comparison literature catalysts whose noble-metal loading respect reached 0.5–1.0 mol % for Ru and a record lowest 0.04 Ir, current catalyst achieves same 0.025 Ru. mechanism acceptorless dehydrogenative condensation (ADC) was proposed on basis DFT calculations; addition, reactive intermediates were determined by GC-MS, NMR, single-crystal X-ray diffraction. catalytic process is potentially suitable industrial applications.

Язык: Английский

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